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X-ray Absorption Studies of Vanadium Valence and Local Environment in Borosilicate Waste Glasses

Published online by Cambridge University Press:  21 March 2011

David A. McKeown
Affiliation:
Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave, N.E., Washington, D.C. 20064
Isabelle S. Muller
Affiliation:
Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave, N.E., Washington, D.C. 20064
Keith S. Matlack
Affiliation:
Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave, N.E., Washington, D.C. 20064
Ian L. Pegg
Affiliation:
Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave, N.E., Washington, D.C. 20064
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Abstract

XANES and EXAFS data were collected and analyzed to characterize vanadium in borosilicate glasses used for immobilization of sulfur-containing nuclear wastes. Earlier studies suggested that adding vanadium to the melt improves sulfur solubility. Data are presented for a variety of borosilicate glasses, some containing sulfur and some sulfur-free, that have V2O5 concentrations as high as 12 wt%, and for crystalline vanadium sulfide, silicate, and oxide standards. The data for all glasses investigated indicate that most or all vanadium has a +5 valence and is tetrahedrally coordinated by oxygen atoms. Both XANES and EXAFS also show that glasses synthesized under reducing conditions can have pentacoordinated V+4 populations up to approximately 20 to 25% of all vanadium present with the remainder being V+5O4. There is no evidence from XANES or EXAFS of V-S bonds in any of the glasses investigated.

Type
Research Article
Copyright
Copyright © Materials Research Society 2002

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